Diazotizable dyestuffs easily soluble in water



UNITED STATES PATENT OFFICE.

HERMANN FRITZSCI-IE, OF BASEL. SWITZERLAND, ASSIGNOR TO SOCIETY OF CHEMI- CAL INDUSTRY IN BASLE, OF BASEL, SWITZERLAND.

DIAZOTIZABLE DYESTUFFS EASILY SOLUBLE IN WATER.

N 0 Drawing.

T 0 all w 710m it may con ca m Be it known that I, HERMANN FnrrZsoHE, a citizen of the Swiss Republic, and resident of Basel, Switzerland, have invented new and useful Diazotizable Dyestuffs Easily Soluble in ater, of which the following is a full, clear, and exact specification.

I have found that by introducing the N-methyl-m-sulforadicals into the substantive azodyestuifs, which can be further diazotized on the fiber and the further diazotizable amino groups of which are bound externally, there are obtained dyestuffs which show relatively to the dyestuffs which are not substituted in the diazotizable amino groups an improved solubility in water without sacrifice of their dyeing power. These dyestuffs constitute in a dry state redbrown to black-brown powders, which dissolve in water and in concentrated sulfuric acid to yellow to violet solutions. Their dyeings on cotton can be diazotized, obviously after the N-methyl-o-sulfo radical is split off, and be developed with non-sulfonated developing compounds, as for instance betanaphthol, metaphenylenediamin, phenylmethylpyrazolone, etc. whereby the dyeings acquire an extraordinary fastness to washing.

Diazotizable dyestuffs containing N- methyl a sulfoderivatives or N -Inethyl'-o sulfonates of external amino groups can be Specification of Letters Patent.

Application filed December 29, 1919. Serial No. 348,213.

prepared by the action of formaldehydebrsulfite on the diazotizable dyestuffs containing at least one external amino group or by combining aromatic diazo-compounds with azodyestufl components containing an external N-metl1yl-o-suforadical.

The invention is illustrated by the following examples:

Example 1.

50 parts of the sodium salt of the amdyestuff derived from betadiazonaphthalene and metaaminobenzoyl-Q-amino-5-oxynaphtlialene-7-sulfonic acid (or the corresponding quantity of the paste obtained in the manufacture of this dyestuff) are diluted and mixed with 300 parts of water and to the mass thus obtained is added a mixture of 52 parts of a solution of sodium bisulfite of 40 per cent. and of 6 parts of formaldehyde in form of an aqueous solution of 30 to 40 per cent., previously heated to boiling. The mass is heated to boiling for about 1 hour, and the dyestuff is precipitated therefrom by an addition of common salt, filtered off, pressed and dried. The N-methylo-sulfonate obtained is a red-brown powder easily soluble in water and dyes unmordanted cotton bluish-red tints becoming fast to washing by diazotizing on the fiber and development with betanaphthol. It corresponds to the formula NHCH SOaNa NaOas NHCO Example 2.

hyde. The mass is boiled until the dyestufi formed is completely dissolved; hereafter this latter is precipitated by addition of connnon salt and isolated as indicated in the foregoing example. The N methyl o sulfonate of the dyestuif constitutesa yellow powder and dyes unmordanted cotton directly yellow tints turning, when diazotized on the fiber and developed with betanaphthol to ,an orange fast to washing and becoming alsofast to washing when diazo-' tized on the fiber and developed with 1- Example 3.

The aqueous solution of the diazoderi'vative of 141.3 .parts of betanaphthylamin is introduced into the cold aqueous solution of 45.3 parts of the N-methyl-m-sulfo-derivative of metaaminobenzoyl-2-amino-5-oxynapht11alene-7-sulfonic acid and of 30 parts of calcined sodium carbonate. The reaction being terminated, the dyest-uff is precipitated by common salt at 50 (3., filtered oit, pressed and dried.

The dyestuif is identical with the dyestufi' of Example 1.

The N-methyl-m-sulf0-metaaminobenzoyl- 2-amino-5-oxynaphthalene-7-sulfonic acid or its disodium salt employed as parent material is prepared by heating for 2.h0urs at 80 to 90 C. 38 parts of sodium Q-metaaminobenzoyl-2-amino-5-oxynaphthalene J7 SllljfOIlEltE with a mixture of 26 parts of solution of sodium bisulfite of 40 per cent. and of an aqueous solution of 6 gr. of formaldehyde. This solution can be employed directly for the preparation of the dyestufi.

Example 4. 22.6 parts of 3.3'-diamino-4:.4:-ditolylmethane (see J OMTIMZZ fair Praktische C. with 13.18 parts of'sodium nitrite. The resulting solution of tetrazocompound is added to an aqueous solution of 90 parts of N-methyl-m-sulfonate of 3-aminophenyl-5- oxy-1.2-naphthimidazol-7-sulfonic acid and 60 parts of calcined sodium carbonate.

The dyestuff salted out at 50 C. and iso lated in the usual manner constitutes a red powder and dyes unmordanted cotton directly claret tints turning, when diazotized on the fiber and developed with betanaphw J M A dyestuff of very similar properties is obtained, When in this example there is substituted for the 3.3'-diamino-4c-4c"-ditolylmethane the equivalent quantity of 3.3-diaminodiphenylmethane. This latter is obtained by complete reduction in the usual manner of the 3.3-dinitrodiphenylmethane described in the German Patent No. 67001.

Ewample- 5.

The solution of tetrazocompound derived from 22.6 parts of 3.3-diaminoditolylmethane according to Example 4 is added to an aqueous solution of 93.5 parts of the methyl-@- sulfo-derivative of the para-aminophenylurea of 2-amino-5-naphtl1ol-7-sulfonic acid and of 60 parts of sodium carbonate. The dyestuff isolated in the usual manner constitutes a dark red powder and dyes cotton directly yellowish-red tints turning, when diazotized on the fiber and developed with betanaphthol, to a claret fast to Washing. It corresponds to the formula OH: OH

The following tabular exhibit shows for a of their direc certain number of dyestuffs able to be prepared according tothe invention the tints t dyeings and of their dyeings diazotized and developed with betanaphthol. 5

What I claim is:

1. ,As new products the herein described Gives a dyestufl dyeing- The dlazoderlvative of- Combined with After diazotizing on the Directly fiber and develo ment with betana'phthoi Paraamlnoacetanllid Methyl-m-sulloderivatlve of the m- Bluish-red tints Bluish-red tints.

am1nobenzoy1-2-amino-5-naphtho1- 7-sulfonic acid.

l-Amino-2-mothoxy-4-methylbenzene... Methyl a: sulfoderivative of the m- .....ld Id.

aminobenzoyl 2 amino 5 naph thol-7-sulfonic acid.

B-Naphthylamin .id .id Id.

m.m'-Diaminodltolylmethane 2 molecules id Yellowish-red tints Plain yellowish-red tints.

m.m-Diaminodiphenylmethane Zmolecnlesid Red-otangetints Reddish-orang e tints.

p.p-Dlaminodiphenylether 2moleculesid Bluish-red tints Red tints.

p-Aminoazobenzene lmoleculeid Blue-red tints Blnish-red tints.

p-Aminoazotoluene(from o-toluidin). lmoleciileid Clarettints Claret tints.

m.m-Diamincditolylmethane 2 molecules methyl-o-sulfoderivative of Yellowish-claret tints Blue-red tints.

the 3'-aminophenyl-5-oxy-1.2- naphthimidazo1-7-su1fonic acid.

m.m-Diaminodiphenylurea ..id Bllli h-red tints Bluish-red tints.

m-Amlnobenzoyl-m-phenylenediamin .id Yellow-red tints Yellow-red tints.

p.p-Diaminodiphenylether ..id Claret tints Claret tints.

Azoxyanilin ..id Blue-red tints .i Yellowish-red tints.

m.m'-Diaminoditolylmethane Methyl-w-sulfoderivative of the p- Yellow-red tints Claret tints.

. aminophenylurea of 2-amino-5-oxynaphthaIenefl-sulfonicacid.

m.m-Diaminoditolylmethane Methyl-w-sulfoderivative of the m- Yellow-red tints Claret tints.

' aminolphenylurea of 2-amino-5-oxynapht alene-7-sulfonic acid.

m-Aminobenzoyl-m-phenylenediamin. 2 molecules methylwsulfoderivative Yellow tints Orange tints.

of m-aminophenylpyrazolone carboxylic acid.

m-m-Diaminodiphenylmethane 2 molecules methyl-w-sulfoderivative Yellow tints Yellow-orange tints. of m-aminophenylpyrazolone carboxylic acid.

2. As new products the herein described substantive azodyestufi's, easily soluble in water and diazotizable on the fiber, which contain an external N-methyl-m-sulforadical, constitute in a dry state red-brown to black-brown powders solublein water and in concentrated sulfonic acid to yellow to violet solutions and dye cotton directly yellow to claret tints becoming extraordinarily fast to washing, when diazotized on the fiber and developed with a non-sulfonated developing compound.

water and diazotizable on the fiber which are derived from the tetrazo-derivative of a diamin corresponding to the formula and constitute in a dry state red-brown to black-brown powders soluble in water and in concentrated sulfuric acid to yellow to violet solutions and dye cotton directly yellow to claret tints becoming extraordinarily fast to washing, when diazotized on the fiber and developed with a non-sulfonated developing compound.

3. As new products the herein described substantive azodyestuffs, easily soluble inv water and diazotizable on the fiber which are derived from the tetrazo derivative of a diamin corresponding to the formula red to violet solutions and dye cotton directly red to claret tints becoming extraordinarily fast to washing, when diazotized on the fiber and developed with a non-sulfonated developing compound.

4. As new products the herein described substantive azodyestuffs, easily soluble in water and diazotizable on the fiber, which are derived from the tetrazoderivative of 3.3-diamino-4.4 dimethyldiphenylmethane and a derivative of 2-amino-5-oxynaphthalene7-sulfonic acid containing an external *-N-methyl-m-sulfo radical, and constitute in a dry state red-brown to black-brown powders soluble in water and in concentrated sulfuric acid to red to violet solutions and dye cotton directly red to claret tints becom-' ing extraordinarily fast to washing, when diazotized on the fiber and developing with a non-sulfonated developing compound.

In witness whereof I have hereunto signed my name this 29th day of November, 1919, in the presence of two subscribing witnesses.

HERMANN FRITZSGHE.

Witnesses VVILLIAM E. HOLLAND, AMAND BRAUN. 

